CN104692678A - Composite desulphurization material for iron-mine waste residues and preparation method thereof - Google Patents
Composite desulphurization material for iron-mine waste residues and preparation method thereof Download PDFInfo
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- CN104692678A CN104692678A CN201510118412.XA CN201510118412A CN104692678A CN 104692678 A CN104692678 A CN 104692678A CN 201510118412 A CN201510118412 A CN 201510118412A CN 104692678 A CN104692678 A CN 104692678A
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- iron ore
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- sulfur removal
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Abstract
The invention discloses a composite desulphurization material for iron-mine waste residues and a preparation method thereof; and the composite desulphurization material is prepared from coal ash, blaster furnace slag, a binding agent, an alumina carrier material, a magnesium carrier material, zinc oxide, silicon dioxide, titanium oxide, calcium oxide in mass ratio. The method comprises the steps: grinding and uniformly mixing the raw materials, then putting into a furnace chamber to heat so as to evaporate free water; adding organic acid, soaking, continuously heating to obtain a sintered body; naturally cooling, smashing and grinding, thereby obtaining powder. The desulphurization material is simple, low in production cost, good in desulphurization effect and capable of effectively protecting the environment; the discharge of mineral waste residues meets the national legal standard and the regional ecological environment is improved; the recycling of industrial wastes is realized, the additional value of waste recovery is added and the recovery cost of sulfur resources is reduced.
Description
Technical field
The present invention relates to technical field of material, specifically a kind of iron ore waste residue composite sulfur removal material and preparation method thereof.
Background technology
The waste residues such as slag, cinder, flyash are the solid waste of the industry discharges such as metallurgy, electric power.Banking up in a large number of these wastes not only wastes land resources, and easily causes environmental pollution.The annual emissions of current China slag reaches more than 1,600 ten thousand tons, and the annual emissions of flyash is about 1,100 ten thousand tons, but its cyclic utilization rate is only about 10%.These waste residues are mainly used as the low value-added Land use models such as road-making material, backfilling material, brick producing material.At present, utilize industrial waste, add appropriate whipping agent and be aided with the additives such as binding agent, composite go out applicable sewage treatment process use efficient except sulfur materials, and realizing the recycling of Sulphur ressource with this, domestic there is not been reported.
Sulphur in current removing slag mainly adopts biological process and chemical method.Biological process desulfurization process is complicated, and stable water outlet is poor; Although chemical method sulphur removal treatment effect is good, application mostly be the Industrial products such as lime, aluminium salt, molysite, ferrous salt and magnesium salts except sulfur materials, due to sulphur removal medicament costly, sludge quantity is comparatively large, causes the bottleneck of this method in production application.Thus develop sulphur high adsorption capacity, there is some strength and chemical stability, flow resistance is little, density is little, that porosity is large, good in economic efficiency is efficient except sulfur materials, and be applied in the chemical desulfurization process of various sewage and slag, sulphur enrichment in sewage being separated, is the important means ensureing sewage sulfur limitation effect, realize Sulphur ressource recycling.
Summary of the invention
The object of the present invention is to provide a kind of iron ore waste residue composite sulfur removal material and preparation method thereof, to solve the problem proposed in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
A kind of iron ore waste residue composite sulfur removal material, formulated according to mass ratio by following raw material: flyash 30 ~ 40%, bottom slag 15 ~ 20%, adhesion agent 10 ~ 15%, alumina supporter material 5 ~ 10%, magnesium carrier material 5 ~ 10%, zinc oxide 5 ~ 10%, silicon-dioxide 2 ~ 5%, titanium oxide 2 ~ 5%, calcium oxide 2 ~ 5%.
As the further scheme of the present invention: described adhesion agent be concrete grey, plaster stone, water glass, white lime one or more.
As the further scheme of the present invention: described alumina supporter material be aluminum oxide, aluminium hydroxide one or both.
As the present invention's further scheme: described magnesium carrier material be magnesium oxide, magnesium hydroxide, magnesiumcarbonate one or both.
A preparation method for iron ore waste residue composite sulfur removal material, concrete preparation process is as follows: (1) according to mass ratio by raw material pulverizing, and add adhesion agent mixing 25 ~ 30min obtain mixed raw material; (2) mixed raw material shaping after put into furnace chamber, be slowly warming up to 110 DEG C, insulation 40 ~ 50min, allow free water evaporation in raw material; (3) adopt the organic acid adding 1% ~ 5%, soak 25 ~ 30min, then continue to be warming up to 1200 DEG C, insulation 90 ~ 100min, stops heating, obtains sintered compact, naturally cool to normal temperature; (4) again its sintered compact is obtained 0.06 ~ 0.08 μm of powder through pulverizing, grinding.
As the further scheme of the present invention: described organic acid is one or both in succsinic acid, oxaloacetic acid, Cyclopropylacetic acid, 4-ethoxy-phenylacetic acid, vinyl sulfonic acid.
Compared with prior art, the invention has the beneficial effects as follows: sweetening material of the present invention is simple, and production cost is low, and sweetening effectiveness is good, effectively can reach protection of the environment, slag discharge reaches national statutory standards, improves region environment; The resource utilization of trade waste can be realized, and added the added value of utilization of waste material, reduce the cost recovery of Sulphur ressource.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A kind of iron ore waste residue composite sulfur removal material, formulated according to mass ratio by following raw material: flyash 40%, bottom slag 15%, adhesion agent 15%, alumina supporter material 5%, magnesium carrier material 10%, zinc oxide 5%, silicon-dioxide 3%, titanium oxide 3%, calcium oxide 4%.
The preparation method of above-mentioned iron ore waste residue composite sulfur removal material, concrete preparation process is as follows: (1) by raw material pulverizing according to mass ratio, and adds adhesion agent mixing 30min and obtains mixed raw material; (2) mixed raw material shaping after put into furnace chamber, be slowly warming up to 110 DEG C, insulation 45min, allow free water evaporation in raw material; (3) adopt the succsinic acid adding 5%, soak 30min, then continue to be warming up to 1200 DEG C, insulation 90min, stops heating, obtains sintered compact, naturally cool to normal temperature; (4) again its sintered compact is obtained 0.06 ~ 0.08 μm of powder through pulverizing, grinding.
Be that 2 ‰ to join sulphur concentration be in the waste water of 50mg/L in mass ratio by the powder mass obtained, after stirring reaction 20min, staticly settle, solid-liquid separation, supernatant liquor discharges, after primary treatment, in water, residual sulphur ionic concn is 1.0mg/L, and lower than the first discharge standard of national regulation, clearance is up to 98.0%.
Embodiment 2
A kind of iron ore waste residue composite sulfur removal material, formulated according to mass ratio by following raw material: flyash 35%, bottom slag 15%, adhesion agent 15%, alumina supporter material 10%, magnesium carrier material 5%, zinc oxide 10%, silicon-dioxide 3%, titanium oxide 4%, calcium oxide 3%.
The preparation method of above-mentioned iron ore waste residue composite sulfur removal material, concrete preparation process is as follows: (1) by raw material pulverizing according to mass ratio, and adds adhesion agent mixing 30min and obtains mixed raw material; (2) mixed raw material shaping after put into furnace chamber, be slowly warming up to 110 DEG C, insulation 45min, allow free water evaporation in raw material; (3) adopt the Cyclopropylacetic acid adding 5%, soak 30min, then continue to be warming up to 1200 DEG C, insulation 90min, stops heating, obtains sintered compact, naturally cool to normal temperature; (4) again its sintered compact is obtained 0.06 ~ 0.08 μm of powder through pulverizing, grinding.
Be that 4 ‰ to join sulphur concentration be in the waste water of 100mg/L in mass ratio by the powder mass obtained, after stirring reaction 30min, staticly settle, solid-liquid separation, supernatant liquor discharges, after primary treatment, in water, residual sulphur ionic concn is 1.0mg/L, and lower than the first discharge standard of national regulation, clearance is up to 99.0%.
Embodiment 3
A kind of iron ore waste residue composite sulfur removal material, formulated according to mass ratio by following raw material: flyash 30%, bottom slag 15%, adhesion agent 10%, alumina supporter material 10%, magnesium carrier material 10%, zinc oxide 10%, silicon-dioxide 4%, titanium oxide 3%, calcium oxide 3%.
The preparation method of above-mentioned iron ore waste residue composite sulfur removal material, concrete preparation process is as follows: (1) by raw material pulverizing according to mass ratio, and adds adhesion agent mixing 30min and obtains mixed raw material; (2) mixed raw material shaping after put into furnace chamber, be slowly warming up to 110 DEG C, insulation 45min, allow free water evaporation in raw material; (3) adopt the vinyl sulfonic acid adding 5%, soak 30min, then continue to be warming up to 1200 DEG C, insulation 90min, stops heating, obtains sintered compact, naturally cool to normal temperature; (4) again its sintered compact is obtained 0.06 ~ 0.08 μm of powder through pulverizing, grinding.
Be that 8 ‰ to join sulphur concentration be in the waste water of 150mg/L in mass ratio by the powder mass obtained, after stirring reaction 40min, staticly settle, solid-liquid separation, supernatant liquor discharges, after primary treatment, in water, residual sulphur ionic concn is 0.5mg/L, and lower than the first discharge standard of national regulation, clearance is up to 99.67%.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
Claims (6)
1. an iron ore waste residue composite sulfur removal material, it is characterized in that, formulated according to mass ratio by following raw material: flyash 30 ~ 40%, bottom slag 15 ~ 20%, adhesion agent 10 ~ 15%, alumina supporter material 5 ~ 10%, magnesium carrier material 5 ~ 10%, zinc oxide 5 ~ 10%, silicon-dioxide 2 ~ 5%, titanium oxide 2 ~ 5%, calcium oxide 2 ~ 5%.
2. iron ore waste residue composite sulfur removal material according to claim 1, is characterized in that, described adhesion agent be concrete grey, plaster stone, water glass, white lime one or more.
3. iron ore waste residue composite sulfur removal material according to claim 1, is characterized in that, described alumina supporter material be aluminum oxide, aluminium hydroxide one or both.
4. iron ore waste residue composite sulfur removal material according to claim 1, is characterized in that, described magnesium carrier material be magnesium oxide, magnesium hydroxide, magnesiumcarbonate one or both.
5. a preparation method for iron ore waste residue composite sulfur removal material as claimed in claim 1, it is characterized in that, concrete preparation process is as follows: (1) according to mass ratio by raw material pulverizing, and add adhesion agent mixing 25 ~ 30min obtain mixed raw material; (2) mixed raw material shaping after put into furnace chamber, be slowly warming up to 110 DEG C, insulation 40 ~ 50min, allow free water evaporation in raw material; (3) adopt the organic acid adding 1% ~ 5%, soak 25 ~ 30min, then continue to be warming up to 1200 DEG C, insulation 90 ~ 100min, stops heating, obtains sintered compact, naturally cool to normal temperature; (4) again its sintered compact is obtained 0.06 ~ 0.08 μm of powder through pulverizing, grinding.
6. the preparation method of iron ore waste residue composite sulfur removal material according to claim 5, is characterized in that, described organic acid is one or both in succsinic acid, oxaloacetic acid, Cyclopropylacetic acid, 4-ethoxy-phenylacetic acid, vinyl sulfonic acid.
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| CN201510118412.XA CN104692678A (en) | 2015-03-18 | 2015-03-18 | Composite desulphurization material for iron-mine waste residues and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963819A (en) * | 2017-12-14 | 2018-04-27 | 马鞍山松鹤信息科技有限公司 | A kind of composite sulfur removal material and its preparation process |
| CN115350694A (en) * | 2022-06-08 | 2022-11-18 | 上海大学 | Method for preparing molded acid gas adsorbent by using iron-containing waste residues and molded acid gas adsorbent prepared by using method |
| CN115445411A (en) * | 2022-07-07 | 2022-12-09 | 南京永能新材料有限公司 | Solid waste powder desulfurizer for cement kiln and preparation method thereof |
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| CN102464393A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Industrial waste residue based composite desulfuration material and application method thereof |
| CN102976460A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Boiler waste slag-based composite dephosphorizing material and application method thereof |
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2015
- 2015-03-18 CN CN201510118412.XA patent/CN104692678A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102464393A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Industrial waste residue based composite desulfuration material and application method thereof |
| CN102976460A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Boiler waste slag-based composite dephosphorizing material and application method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963819A (en) * | 2017-12-14 | 2018-04-27 | 马鞍山松鹤信息科技有限公司 | A kind of composite sulfur removal material and its preparation process |
| CN115350694A (en) * | 2022-06-08 | 2022-11-18 | 上海大学 | Method for preparing molded acid gas adsorbent by using iron-containing waste residues and molded acid gas adsorbent prepared by using method |
| CN115350694B (en) * | 2022-06-08 | 2024-03-19 | 上海大学 | Method for preparing formed acid gas adsorbent by utilizing iron-containing waste residues and formed acid gas adsorbent prepared by method |
| CN115445411A (en) * | 2022-07-07 | 2022-12-09 | 南京永能新材料有限公司 | Solid waste powder desulfurizer for cement kiln and preparation method thereof |
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Application publication date: 20150610 |